US4937320A - Dimerized fatty acid having a high content of dicarboxylic acid - Google Patents

Dimerized fatty acid having a high content of dicarboxylic acid Download PDF

Info

Publication number
US4937320A
US4937320A US07/304,599 US30459989A US4937320A US 4937320 A US4937320 A US 4937320A US 30459989 A US30459989 A US 30459989A US 4937320 A US4937320 A US 4937320A
Authority
US
United States
Prior art keywords
dicarboxylic acid
acid
fatty acid
groups
dicarboxylic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US07/304,599
Inventor
Johannes J. Vreeswijk
Klaus D. Haase
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Uniqema BV
Original Assignee
Unilever Patent Holdings BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
Priority to NL8700862A priority Critical patent/NL194372C/en
Priority to NL8700862 priority
Application filed by Unilever Patent Holdings BV filed Critical Unilever Patent Holdings BV
Application granted granted Critical
Publication of US4937320A publication Critical patent/US4937320A/en
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=19849845&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=US4937320(A) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Assigned to UNICHEMA CHEMIE B.V. reassignment UNICHEMA CHEMIE B.V. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: UNILEVER PATENT HOLDLINGS B.V.
Anticipated expiration legal-status Critical
Application status is Expired - Lifetime legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C57/00Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
    • C07C57/02Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C07C57/13Dicarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/46Polyesters chemically modified by esterification
    • C08G63/48Polyesters chemically modified by esterification by unsaturated higher fatty oils or their acids; by resin acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/52Polycarboxylic acids or polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/34Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids using polymerised unsaturated fatty acids

Abstract

The invention provides a dimerized fatty acid with a content of dicarboxylic acid of at least 97.5 wt. %, preferably at least 98.5 wt. %.
Also provided is a process for the preparation of a pure dimerized fatty acid in which a fatty acid that has been dimerized is freed, by a physical method, of fractions having predominantly monocarboxyic acids and tricarboxylic acids.
The invention further provides a high molecular weight polymer which contains groups derived from a C4 -C12 dicarboxylic acid and approximately equimolar amounts of dicarboxylic acids and diamines and/or diols which are converted while volatile reaction products are removed.

Description

This is a division of application Ser. No. 07/083,195, filed Aug. 10, 1987.

The application relates to dimerised fatty acids having a high content, i.e. at least 97.5 wt. %, of dicarboxylic acid, as well as to polymers which contain groups derived from such pure dimeric fatty acids. As such polymers, especially polyamides, polyesters, polyester-amides and polyether-amides are meant, but also polyurethan for example.

The commercially available dimerised fatty acids mostly contain approximately 15 to 25 wt. % trimer (T) and higher oligomers and 1 to 5 wt. % monomer (M) and the remainder is often regarded as dimer (D). The terms monomer, dimer and trimer are in this case based more on the molecular weight than on the functionality, i.e. the number of carboxyl groups per molecule. Therefore, a dimeric fatty acid that has lost a carboxyl group through decarboxylation is regarded here as dimer (D), while according to the present application it does not count as dicarboxylic acid but, on the contrary, is regarded as monocarboxylic acid.

Furthermore, from GB-A- 999 732 (General Mills Inc.) purified polymeric fatty acids are known which are "water white" and have a relatively high content of dimer (D), as that is determined by short way distillation of polymerised fatty acids according to Paschke (J.A.O.C.S. 31 (1954), 5-7). According to this method, however, among other things a certain amount of cracking of the residue takes place, as a result of which the percentages of trimer determined in this way are lower than in reality. A more reliable method of determining the contents of monocarboxylic acid, dicarboxylic acid and tricarboxylic acid is by means of gas-liquid chromatography (GLC) as described in the thesis of M.J.A.M. den Otter, The clay-catalyzed dimerisation of oleic acid, pages 52-55, Technische Hogeschool Eindhoven, The Netherlands, 1968.

The methodology of GLC determination described in this thesis was also used according to the present application and gives values which are directed to the number of carboxyl groups rather than to the molecular weight. The percentages of trimer in the British patent application cited are consequently considerably lower than the percentages of tricarboxylic acid which are determined by the GLC method and differences of several percent have been observed. The percentages of trimer mentioned in this patent application on page 7 are considered to be unrealistically low and the products mentioned there are consequently not damaging to the novelty of the dimeric fatty acids having a weight percentage of more than 97.5 or of the 98.5 of dicarboxylic acid according to the present invention. Also in EP-A- 22 048 (Rhone Poulenc Ind.) polyamides are disclosed which are based on hydrogenated, fractionated, polymerised fatty acids which are said to contain more than 95% by weight of "dimer". These polyamides allegedly have favourable properties like: homogeneity, transparency, toughness, hydrolysis stability and thermal resistance.

The present application now claims rights for, inter alia, a dimerised fatty acid having a dicarboxylic acid content of more than 97.5% by weight, preferably more than 98.5% by weight, more preferably more than 99.0% by weight. Dimerised fatty acids having such high contents of dicarboxylic acid can be obtained by fractionation, with a physical method, of a fatty acid that has been dimerised according to a method known per se until a fraction has been obtained having the desired percentage of dicarboxylic acid.

For the dimerisation of fatty acids, as a rule unsaturated fatty acids--or mixtures thereof--are used which contain 16 to 22 carbon atoms in the molecule.

The dimerisation normally takes place at temperatures between 180° and 270° C. under water vapour pressure and in the presence of approximately 2 to 10% clay catalyst. This process is also described in GB-A-1 050 148 (General Mills Inc.). The fractionation of the dimerised product can be effected in various ways, but distillation under high vacuum at increasing temperature (molecular distillation) is a suitable method. Extraction methods can also be used, in particular supercritical extraction. Optionally, the dimerised fatty acid can also be hydrogenated, as described, for example, in GB-A- 999 730.

The present application furthermore claims rights for polymers, particularly high polymeric materials, in which dimerised fatty acid having a percentage of more than 97.5, preferably more than 98.5% or more preferably even more than 99.0% of dicarboxylic acid has been incorporated. This dicarboxylic acid that, depending on the starting fatty acid, contains from 32 to 44 carbon atoms in the molecule, imparts to a high polymer, in the purity mentioned, an exceedingly favourable combination of mechanical properties, such as a good tensile strength and elasticity, good low temperature impact resistance and the good dimension stability because of low water absorption. Thus it has been found, for example, that the tensile strength of a polyamide based on hexamethylenediamine and dimer having 99% dicarboxyl acid is much better than that of a corresponding polyamide based on dimer having 95% dicarboxylic acid; also with respect to flexibility, the first polymer is better than the second.

In order to obtain favourable properties in the polyamide, for e.g. hot-melt bonding, it is sometimes desirable to prepare polyamides with combinations of diamines, for example combinations of ethylenedamine (EDA) and hexamethylenediamine (HMDA), namely in ratios of 20/80 to 80/20, preferably in ratios of 60/40 to 40/60 molar.

Also aromatic amines like piperazine can be used in addition in order to obtain special effects. As a rule the diamine contains 2 to 9 carbon atoms. For high-quality plastics it is particularly advantageous to include caprolactam in the polyamide.

Besides the pure dimer according to the present invention, another (co-) dicarboxylic acid can be used. Suitable dicarboxylic acids are particularly those which contain between 4 and 12 carbon atoms, both aliphatic and aromatic dicarboxylic acids being suitable. Here the molar ratio between dimeric acid according to the invention and other dicarboxylic acid lies between 20/80 and 80/20, preferably between 60/40 and 40/60. Besides diamines, also difunctional ether-amines and ester-amines or blocks thereof can be built in. Both high molecular polyamides and lower, reactive polyamides having, for example, terminal carboxyl groups are encompassed.

The present application also provides polyesters, in particular high molecular polyesters, which contain dimerised fatty acid according to the present invention, as well as C2 -C6 diols, optionally together with other above-mentioned dicarboxylic acids; polyether diols can also be incorporated in addition. For these high polymers, attention is drawn in particular to the favourable combination of a high melting viscosity and good flexibility. Besides high polymeric polyesters, the present invention also provides lower molecular polyesters having terminal carboxyl groups, which can be excellently hardened with polyepoxides to particularly good, flexible coatings.

The polymers, particularly the high molecular weight polymers, according to this embodiment of the invention can be prepared in a manner known per se by converting dimeric fatty acids having a high content of dicarboxylic acid (or a functional derivative thereof such as, for example, dimethylester) with at least one diamine/diol and/or ether diamine, optionally in the presence of another dicarboxylic acid, while removing the volatile components formed, such as water or methanol.

Unlike the case with the preparation of the conventional polymers, it is noticeable with this process that, during the cooking, there is little or rather no danger of the reaction mixture starting to gel and thus becoming unmanageable or of the molecular weight not being able to increase sufficiently because of the presence of too much monocarboxylic acid. For the preparation of high polymers, of course, equimolar amounts of dicarboxylic acid and diamine/diol and optionally ether diol are used, or sometimes a small excess of volatile reaction component, which excess is eventually distilled off.

The invention is illustrated by the following examples:

EXAMPLE 1

The commercially available dimerised fatty acid PRIPOL 1017, ex Unichema, Gouda, was separated via a so-called molecular distillation into a fraction which contained mainly difunctional fatty acids. The separation of the monofunctional material was carried out at a temperature of 240° C. and a pressure of 0.005 mm Hg, while hereafter the difunctional carboxylic acid was distilled over at a temperature of 280° C. and a pressure of 0.002 mm Hg. This fraction was hydrogenated with a Pd on carbon carrier as catalyst at a pressure of 2.5 MPa and a temperature of 180° C. for 5 hours. The hydrogenated product was subsequently separated again with the aid of a so-called molecular distillation apparatus. During the molecular distillation, first of all monofunctional fatty acids were separated at a temperature of 280° C. and a pressure of 0.001 mm Hg. In Table 1 the compositions of the most important products after the different process steps are summarized.

              TABLE 1______________________________________              fraction after     PRIPOL   molecular distillation     1017     first time                       second time______________________________________less thandifunctional (wt. %)       7.1        2.5      0.5difunctional (wt. %)       72.0       93.5     99.0higher thandifunctional (wt. %)       2l.0       4.0      0.5iodine value (Weiss)       98         98       9______________________________________
EXAMPLES 2-7

A commercial product comparable with those described in BG-A-999 732 is PRIPOL 1010 (ex Unichema, Gouda), that has the composition as given in Table 2.

              TABLE 2______________________________________         PRIPOL 1010         (composition in wt. %)______________________________________less than difunctional           1.5difunctional    95.5higher than difunctional           3.0iodine value (Weiss)           6______________________________________

Polyamides were prepared from the above-mentioned purified, dimerised fatty acids. The process for the preparation of these polyamides is: reacting the dimerised fatty acid for 5 hours at 220° C. with an equivalent amount of diamine, using 0.03 wt. % phosphoric acid as catalyst and applying a vacuum of 20 mm Hg for the last hour.

The following polyamides were prepared (Table 3):

              TABLE 3______________________________________                     amounts used                     (grams)Type dimer  Type amine    dimer   amine______________________________________1     1010      EDA           507.6 53.62     (*)       EDA           507.6 53.63     (*)       EDA           507.6 53.64     (*)       HMDA (60%)    400   136.55     1010      HMDA (60%)    400   136.5______________________________________ (*)dimer as prepared according to Example 1.

The most important characteristics of the polyamides are summarized in Table 4.

              TABLE 4______________________________________                                Tensile                          Proces-                                strength                                       Elas-                Viscosity sing  at     ti-Acid    Amine   (Pas) at  temp. rupture                                       cityEx.  value   value   230° C.                      190° C.                            °C.                                  MPa    (%)______________________________________1    2.8     1.8     12    39    110   26     4702    1.8     2.2     21    103   114   35     5503    3.5     1.3     18    76.5  115   36     5504    3.3     0.7     89    290    92   35     540______________________________________

Claims (7)

We claim:
1. A polymer that contains groups derived from dimerised fatty acid, in which the dimerised fatty acid groups consist of at least 97.5 wt. % of dicarboxylic acid radicals.
2. A high polymer according to claim 1, in which the dicarboxylic acid groups are built into a polyamide.
3. A polyamide according to claim 1, in which the polyamide contains groups of a C2 -C9 alpha-omega-diamine.
4. A high molecular weight polymer according to claim 1, in which the dicarboxylic acid groups are built into a polyester.
5. A high polymer according to any one of the claims 1, 2 or 4, in which the polymer also contains groups derived from a C4 -C12 dicarboxylic acid.
6. A high polymer according to claim 1, in which the polymer contains in the chain not only amide groups but also ester and/or ether groups.
7. A process for the preparation of a polymer according claim 1, wherein approximately equimolar amounts of dicarboxylic acids and diamines and/or diols are converted with each other while volatile reaction products are removed until the desired polymer has been obtained, characterized in that the dicarboxylic acid consists at least partly of dimerised fatty acids having a content of more than 97.5 wt. % dicarboxylic acid.
US07/304,599 1987-04-13 1989-02-01 Dimerized fatty acid having a high content of dicarboxylic acid Expired - Lifetime US4937320A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
NL8700862A NL194372C (en) 1987-04-13 1987-04-13 Dimerised fatty acids with a high content of dicarboxylic acid.
NL8700862 1987-04-13

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US07083195 Division 1987-08-10

Publications (1)

Publication Number Publication Date
US4937320A true US4937320A (en) 1990-06-26

Family

ID=19849845

Family Applications (1)

Application Number Title Priority Date Filing Date
US07/304,599 Expired - Lifetime US4937320A (en) 1987-04-13 1989-02-01 Dimerized fatty acid having a high content of dicarboxylic acid

Country Status (7)

Country Link
US (1) US4937320A (en)
JP (2) JPS63258830A (en)
BR (1) BR8801419A (en)
DE (2) DE3744995C2 (en)
FR (1) FR2613714B1 (en)
GB (1) GB2203425B (en)
NL (1) NL194372C (en)

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040220357A1 (en) * 2002-08-27 2004-11-04 Shenshen Wu Compositions for golf equipment
US20040220371A1 (en) * 2002-08-27 2004-11-04 Shenshen Wu Compositions for golf equipment
US20040220356A1 (en) * 2002-08-27 2004-11-04 Shenshen Wu Compositions for golf equipment
US20040220378A1 (en) * 2002-08-27 2004-11-04 Manjari Kuntimaddi Compositions for golf equipment
US20040220377A1 (en) * 2002-08-27 2004-11-04 Manjari Kuntimaddi Compositions for golf equipment
US20040220375A1 (en) * 2002-08-27 2004-11-04 Shenshen Wu Compositions for golf equipment
US20040220373A1 (en) * 2002-08-27 2004-11-04 Shenshen Wu Compositions for golf equipment
US20040220376A1 (en) * 2002-08-27 2004-11-04 Manjari Kuntimaddi Compositions for golf equipment
US20050004325A1 (en) * 2002-08-27 2005-01-06 Shenshen Wu Compositions for golf equipment
US20050143525A1 (en) * 2002-07-15 2005-06-30 Shenshen Wu Compositions for golf balls
US20050272909A1 (en) * 2004-06-02 2005-12-08 Manjari Kuntimaddi Compositions for golf equipment
US20050272899A1 (en) * 2004-06-02 2005-12-08 Shenshen Wu Compositions for golf equipment
US20050272530A1 (en) * 2004-06-02 2005-12-08 Shenshen Wu Compositions for golf equipment
US20050272529A1 (en) * 2004-06-02 2005-12-08 Shenshen Wu Compositions for golf equipment
US20050272900A1 (en) * 2004-06-02 2005-12-08 Manjari Kuntimaddi Compositions for golf equipment
US20060231183A1 (en) * 2000-06-14 2006-10-19 Antonio Serra Process for producing tyres, tyres thus obtained and elastomeric compositions used therein
US20070093317A1 (en) * 2002-08-27 2007-04-26 Shenshen Wu Compositions for Golf Equipment
US20080125247A1 (en) * 2004-06-02 2008-05-29 Murali Rajagopalan Compositions for Golf Equipment
US7501479B2 (en) 2007-05-07 2009-03-10 Pittsburg State University Cationic polymerization of biological oils with superacid catalysts
US20110136587A1 (en) * 2003-05-09 2011-06-09 Shawn Ricci Golf balls comprising thermoplastic or thermoset composition having controlled gel time
CN102597052A (en) * 2009-09-22 2012-07-18 帝斯曼知识产权资产管理有限公司 Cooking bag and use of the cooking bag for cooking food

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4121111A1 (en) * 1991-06-26 1993-01-07 Henkel Kgaa Thermoplastically processable polymergemic based on renewable raw materials and method for the production thereof
DE102006057373B3 (en) 2006-12-04 2007-10-18 Byk-Chemie Gmbh Use of polyamide produced by a diamine and a dicarboxylic acid, in a formulation for defoaming aqueous media
CN102066446B (en) 2008-04-17 2013-12-04 陶氏环球技术有限责任公司 Producing polyurethane elastomers from renewable resources
CN104583269B (en) * 2012-08-28 2017-09-01 巴斯夫涂料有限公司 Polymer coating in the multi-color and / or effect paint systems in
JP6419150B2 (en) * 2013-03-25 2018-11-07 ディーエスエム アイピー アセッツ ビー.ブイ.Dsm Ip Assets B.V. Clothes, including a fabric that includes an elastic fiber
DE102017208511A1 (en) 2017-05-19 2018-11-22 Henkel Ag & Co. Kgaa Polyurethane-based binder system

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1050148A (en) * 1964-02-10 1900-01-01
US2793219A (en) * 1954-12-13 1957-05-21 Emery Industries Inc Process of dimerizing monounsaturated fatty acids
US2955121A (en) * 1959-08-24 1960-10-04 Emery Industries Inc Polymerization of unsaturated fatty acids
US2964545A (en) * 1953-03-09 1960-12-13 Gen Mills Inc Dimeric fatty acids and esters thereof
GB999732A (en) * 1962-03-01 1965-07-28 Gen Mills Inc Decolourising polymeric fatty acids
US3900436A (en) * 1971-06-11 1975-08-19 Schering Ag Polyesteramide resin
US4045389A (en) * 1975-07-31 1977-08-30 Schering Aktiengesellschaft Method of adhering textiles with a polyamide melt adhesive
US4396759A (en) * 1980-07-31 1983-08-02 Schering Aktiengesellschaft Method of adhering textiles
US4397991A (en) * 1981-04-24 1983-08-09 Schering Aktiengesellschaft Polyesteramide adhesives and sealing compounds
US4480086A (en) * 1983-09-09 1984-10-30 Eastman Kodak Company Radiation-resistant copolyesters

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB296079A (en) * 1927-08-26 1929-11-29 Oel Und Fett Chemie G M B H An improved method of obtaining fatty acids wholly or almost wholly free from unsaponifiable matter
GB878985A (en) * 1958-01-21 1961-10-04 Wolf Ltd Victor Improvements in or relating to the manufacture of polymeric fatty acids
NL125565C (en) * 1964-01-28
US4062820A (en) * 1976-12-06 1977-12-13 Emery Industries, Inc. Thermoplastic reinforcing adhesives and substrates coated therewith
FR2459810B1 (en) * 1979-06-26 1983-10-21 Rhone Poulenc Ind
EP0040926B1 (en) * 1980-05-13 1984-10-10 N.V. Raychem S.A. Polyamide adhesive compositions and methods for their production, uses of such compositions, and joints and articles including such compositions
DE3504804A1 (en) * 1985-02-13 1986-08-14 Henkel Kgaa melt adhesive
DE3535732A1 (en) * 1985-10-07 1987-04-09 Henkel Kgaa Melt adhesive mixture

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2964545A (en) * 1953-03-09 1960-12-13 Gen Mills Inc Dimeric fatty acids and esters thereof
US2793219A (en) * 1954-12-13 1957-05-21 Emery Industries Inc Process of dimerizing monounsaturated fatty acids
US2955121A (en) * 1959-08-24 1960-10-04 Emery Industries Inc Polymerization of unsaturated fatty acids
GB999732A (en) * 1962-03-01 1965-07-28 Gen Mills Inc Decolourising polymeric fatty acids
GB1050148A (en) * 1964-02-10 1900-01-01
US3900436A (en) * 1971-06-11 1975-08-19 Schering Ag Polyesteramide resin
US4045389A (en) * 1975-07-31 1977-08-30 Schering Aktiengesellschaft Method of adhering textiles with a polyamide melt adhesive
US4396759A (en) * 1980-07-31 1983-08-02 Schering Aktiengesellschaft Method of adhering textiles
US4397991A (en) * 1981-04-24 1983-08-09 Schering Aktiengesellschaft Polyesteramide adhesives and sealing compounds
US4480086A (en) * 1983-09-09 1984-10-30 Eastman Kodak Company Radiation-resistant copolyesters

Cited By (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060231183A1 (en) * 2000-06-14 2006-10-19 Antonio Serra Process for producing tyres, tyres thus obtained and elastomeric compositions used therein
US20090229720A1 (en) * 2000-06-14 2009-09-17 Pirelli Pneumatici S.P.A. Process for producing tyres, tyres thus obtained and elastomeric compositions used therein
US20050143525A1 (en) * 2002-07-15 2005-06-30 Shenshen Wu Compositions for golf balls
US7014574B2 (en) 2002-07-15 2006-03-21 Acushnet Company Compositions for golf balls
US20080064527A1 (en) * 2002-08-27 2008-03-13 Shenshen Wu Compositions for golf equipment
US20040220375A1 (en) * 2002-08-27 2004-11-04 Shenshen Wu Compositions for golf equipment
US20040220373A1 (en) * 2002-08-27 2004-11-04 Shenshen Wu Compositions for golf equipment
US20040220376A1 (en) * 2002-08-27 2004-11-04 Manjari Kuntimaddi Compositions for golf equipment
US20050004325A1 (en) * 2002-08-27 2005-01-06 Shenshen Wu Compositions for golf equipment
US20040220377A1 (en) * 2002-08-27 2004-11-04 Manjari Kuntimaddi Compositions for golf equipment
US7709590B2 (en) 2002-08-27 2010-05-04 Acushnet Company Compositions for golf equipment
US20040220378A1 (en) * 2002-08-27 2004-11-04 Manjari Kuntimaddi Compositions for golf equipment
US7550549B2 (en) 2002-08-27 2009-06-23 Acushnet Company Compositions for golf equipment
US20080188326A1 (en) * 2002-08-27 2008-08-07 Acushnet Company Compositions for Golf Equipment
US7378483B2 (en) 2002-08-27 2008-05-27 Acushnet Company Compositions for golf equipment
US20040220356A1 (en) * 2002-08-27 2004-11-04 Shenshen Wu Compositions for golf equipment
US7098274B2 (en) 2002-08-27 2006-08-29 Acushnet Company Compositions for golf equipment
US7101951B2 (en) 2002-08-27 2006-09-05 Acushnet Company Compositions for golf equipment
US7105628B2 (en) 2002-08-27 2006-09-12 Acushnet Company Compositions for golf equipment
US7105623B2 (en) 2002-08-27 2006-09-12 Acushnet Company Compositions for golf equipment
US7115703B2 (en) 2002-08-27 2006-10-03 Acushnet Company Compositions for golf equipment
US20040220371A1 (en) * 2002-08-27 2004-11-04 Shenshen Wu Compositions for golf equipment
US7138476B2 (en) 2002-08-27 2006-11-21 Acushnet Company Compositions for golf equipment
US7138475B2 (en) 2002-08-27 2006-11-21 Acushnet Company Compositions for golf equipment
US7138477B2 (en) 2002-08-27 2006-11-21 Acushnet Company Compositions for golf equipment
US7157545B2 (en) 2002-08-27 2007-01-02 Acushnet Company Compositions for golf equipment
US20070093317A1 (en) * 2002-08-27 2007-04-26 Shenshen Wu Compositions for Golf Equipment
US20040220357A1 (en) * 2002-08-27 2004-11-04 Shenshen Wu Compositions for golf equipment
US20110136587A1 (en) * 2003-05-09 2011-06-09 Shawn Ricci Golf balls comprising thermoplastic or thermoset composition having controlled gel time
US7256249B2 (en) 2004-06-02 2007-08-14 Acushnet Company Compositions for golf equipment
US7265195B2 (en) 2004-06-02 2007-09-04 Acushnet Company Compositions for golf equipment
US7276570B2 (en) 2004-06-02 2007-10-02 Acushnet Company Compositions for golf equipment
US7253242B2 (en) 2004-06-02 2007-08-07 Acushnet Company Compositions for golf equipment
US20050272900A1 (en) * 2004-06-02 2005-12-08 Manjari Kuntimaddi Compositions for golf equipment
US20050272909A1 (en) * 2004-06-02 2005-12-08 Manjari Kuntimaddi Compositions for golf equipment
US20050272529A1 (en) * 2004-06-02 2005-12-08 Shenshen Wu Compositions for golf equipment
US7253245B2 (en) 2004-06-02 2007-08-07 Acushnet Company Compositions for golf equipment
US20050272530A1 (en) * 2004-06-02 2005-12-08 Shenshen Wu Compositions for golf equipment
US20050272899A1 (en) * 2004-06-02 2005-12-08 Shenshen Wu Compositions for golf equipment
US20080125247A1 (en) * 2004-06-02 2008-05-29 Murali Rajagopalan Compositions for Golf Equipment
US7501479B2 (en) 2007-05-07 2009-03-10 Pittsburg State University Cationic polymerization of biological oils with superacid catalysts
US8013088B2 (en) 2007-05-07 2011-09-06 Pittsburg State University Cationic polymerization of biological oils
US20090309064A1 (en) * 2007-05-07 2009-12-17 Mihail Ionescu Cationic polymerization of biological oils
CN102597052B (en) 2009-09-22 2014-04-09 帝斯曼知识产权资产管理有限公司 Cooking bag and use of cooking bag for cooking food
CN102597052A (en) * 2009-09-22 2012-07-18 帝斯曼知识产权资产管理有限公司 Cooking bag and use of the cooking bag for cooking food

Also Published As

Publication number Publication date
FR2613714B1 (en) 1990-08-31
JPS63258830A (en) 1988-10-26
NL8700862A (en) 1987-07-01
GB8803422D0 (en) 1988-03-16
GB2203425A (en) 1988-10-19
DE3723264A1 (en) 1988-11-03
JPH07113007A (en) 1995-05-02
FR2613714A1 (en) 1988-10-14
DE3744995C2 (en) 1993-03-18
JP2506025B2 (en) 1996-06-12
BR8801419A (en) 1988-11-01
NL194372C (en) 2002-02-04
GB2203425B (en) 1991-03-20
NL194372B (en) 2001-10-01

Similar Documents

Publication Publication Date Title
US3499853A (en) Polyamides
CA1070445A (en) Process for the separation of copolyesteramides used as moldable compositions
CA2060269C (en) Polyether polyamides and process for synthesizing the same
US4269742A (en) Epoxy resin hardening agents from Mannich bases and method for curing
US5631343A (en) Enzymatic synthesis
AU648393B2 (en) Block polyetheramides, process for their synthesis
EP0281461B1 (en) Polyester amides and polyether ester amides; process for their preparation
US5296556A (en) Three-component curable resin compositions
KR970000487B1 (en) Polyamides and objects obtained therefrom
US2789968A (en) Polycarbonates from polymethylene glycol-bis
JP3242781B2 (en) Polyamide resin
US2379413A (en) Amides of high molecular weight carboxylic acids
AU612416B2 (en) Transparent polyamides, process for their manufacture
EP0201434B1 (en) Technical copolyether amides remaining pliable at a low temperature
US2482761A (en) Polymerization of unsaturated fatty acids
EP0188542B1 (en) Blends of polyamides and ethylene polymers carboxylic acid groups
US4062819A (en) Polyamide blends having improved processing characteristics
SU1155160A3 (en) Method of obtaining polyesteramides
US4611051A (en) Novel poly(ester-amide) hot-melt adhesives
US4128525A (en) Thermoplastic adhesives
US4207410A (en) Method for the preparation and use of polyether ester amides with units of the starting components randomly distributed in the polymer chain
EP1297050B1 (en) Block copolyester
US3622604A (en) Synthetic polyamides of a dimeric fatty acid, a lower aliphatic carboxylic acid ethylene diamine, and a co-diamine
US4082708A (en) Adhesive systems comprising a bisamino piperazine-containing polyamide
EP0288331A1 (en) Polyetherthioether ester amides; process for their preparation

Legal Events

Date Code Title Description
STCF Information on status: patent grant

Free format text: PATENTED CASE

FPAY Fee payment

Year of fee payment: 4

FPAY Fee payment

Year of fee payment: 8

AS Assignment

Owner name: UNICHEMA CHEMIE B.V., NETHERLANDS

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:UNILEVER PATENT HOLDLINGS B.V.;REEL/FRAME:009596/0878

Effective date: 19981002

FPAY Fee payment

Year of fee payment: 12